Polyalkylated monohydroxy cyclic sulfones



Patented Sept. 27, 1949 V I i UNITED. STATES TENT "owes POLYALKYLATED MONOHYDROXY CYCLIC SULFON ES Rupert 0.. Morris and Norton 0. Melchior, Berkeley, Calif., assignors to Shell'Developmcnt Company, San Francisco, Calif., a corporation of Delaware No Drawing. ApplicationMay 4, 1946, Serial No. 667,483

12 Claims. (Cl. 260-329) 1' 2 This invention relates to a novel and particudroxy polyalkylsulfolenes may be represented by larly useful class of compounds comprising the the formulae polyalkylated monohydroxy cyclic sulfones. More R particularly; the invention pertains to polyalkylated monohydroxysulfolanes and polyalkyl- 5 =Z ated monohydroxysulfolenes. A particularly and valuable group of compounds comprises the R s R R s monohydroxy-2,4-dialkyl sulfolanes and monohydroxy-2,4-dialkylsuliolenes.

The monohydroxy compounds of the invention 10 wherein one of the Rs is the hydroxy radical,

comprise a five-member'ed heterocyclic nucleus t least t of t di l represented by R consisting f r nuclear Carbon atoms and 3 and/or R1 are alkyl radicals, and the remaining sulfonyl radical and have at, least two alkyl radiand are members f t group tcals directly attached to one or more of the num of t hydrogen t and t organic t. clear carbon'atoms, and'have one hydroxy radical cats,

attached to a satura-tednuclear carbon A aluable group of polyalkylated monohyatom. droxy cyclic sulfones of the invention comprises e el mOHOhYdIOXY-polyalkylsulfolanes Of those compounds containing a five-membered th invention p s a fiv -m mb red h ter heterocyclic ring consisting of four nuclear carcyclic ring consisting'of 'four saturated nuclear bon atoms and a sulfonyl radical and having carbon atoms and a sulfonyl, radical, have at two alkyl radicals directly attached to two difleast tWO alkyl ra cal di tly a fi ch d to on ferent nuclear carbon atoms, preferably in the or more of the nuclear carbon atoms, and have 2- and the i-positionswherein one of the four one of the nuclear carbon atoms'directly attached nuclear carbon atoms is directly attached to the to a hydroxy radical, the remaining free bonds hydroXy radical and wherein the remaining free of the nuclear carbon atoms being directly atbonds of the nuclear carbon atoms are directly tached to members of the group consisting of attached to hydrogen atoms.

the hydrogen atom and organic radicals. The The alkyl radicals which are directly attached monohydroxy polyalkylsulfolanes may be repto the cyclic sulione nucleus are preferably lower resented by the formula alkyl radicals containing not more than four carbon atoms, i. e. the methyl, ethyl, propyl, isof propyl, n-butyl, seo-butyl and tert-butyl radicals. However, useful compounds are also formed L wherein alkyl radicals containing more than four carbon atoms are directly attached to the cyclic R R sulfone nucleus. Examples of the higher alkyl 0 0 radicals are amyl, hexyl, isoamyl, 2-methylamyl,

heptyl, octyl, stearyl, and the like, preferably containing not more than 18 carbon atoms. I

The other organic radicals which may be attached to the nuclear carbon atoms may be hydrocarbon radicals or substituted hydrocarbon radicals, such as the halogen-substituted hydrocarbon radicals. The organicradicalsWhichRmay invention comprise a five-membered heterocyclic represent may be cyclic or acyclic, saturated, ring consisting of four nuclear carbon atoms and r Saturated or aromatic, and include t alkyl, my], a sulfonyl radical, have a double bond between alkenyl, aralkyl aralkenyl alkenaryl cyclotwo vicinal nuclear carbon atoms, have at least alkyl, cycloalkenyl and heterooyclic radicals such two alkyl groups directly attached to one or more as methyl t 1 propyl jsoprgpyl butyl, of the nuclear carbon atoms and one of the nubutyl, sec-butyl, tert-butyl, amyl, hexyl vinyl, Clear c n atoms ly attached to the hyallyl, methallyl, crotyl, butadienyl, phenyl, chlo- -droxy radi al, the rem inin f e b nd of h romethyl, chlorobutyl, .chlorohexyl, chloroallyl, nuclear carbon atoms being directly. attached to 'bromophenyl, chlorophenyl, bromostearyl, dimembers of the group consisting of the hydrogen chlorophenyl, pentachlorophenyl, xylyl, benzyl, atom and the organic radicals. The monohystyryl, cinnamyl, sulfolanyl, 2,4-dimethyl-3-sulwherein one of the Rs is the hydroxy radical, at least two of the R's are'alkyl radicals, and 40 the remaining Rs are members of the group consisting of the hydrogen atom and the organic radicals.

The monohydroxy polyalkyl sulfolenes of the ical of saturated characten. ii e; not readily hydrogenatable, such as the alkyl, cycloalkyl, aryl, aralkyl and alkaryl radicals. Examples of the saturated hydrocarbon. radicals. include methyl, ethyl, propyl, isopropyl; butyL, isobutyl,

sec-butyl, tert-butyl, cyclohexyl, cyclopropyl, phenyl, xylyl, benzyl, oresyl and. 3,3,5-trimethylcyclohexyl.

Monohydroxy polyalkylsulfolanes and monohydroxy polyalkylsulfolenes having the; hydroxy radical on the nuclear carbon atom in the 3- position. and having an alkyl group on each of the nuclear carbon atoms in the 2- and l-positions, possess unexpectedly valuable properties which make them of particular use in various industrial applications. An example of a particularly valuable 2;4-dialkyl:-3 sulfolanol. is 2,4-climethyl-3- sulfolanol.

The numbering system of the sulf'olane or sulfolene ring isindicated below:

-ao--- o4. 2o c5 s1 This isin. accordance with the accepted. system of numbering as exemplified by the compounds oil this type-oi ring structuregiven onpage l4 of Patterson and. Gapell, The Ring; Index,.Reinhold Publishing Corp, New York, 1940; Am. Chem. Soc. Monograph No. 84. The systemmay be exemplified by the compound having the structure CH3-'HG--GH'OH Hz H-CH;

11 ch ats istermed. 2,4-dimethyl-4-sulfolen-3-ol.

t. has, surprisingly, been found. thatithe novel comp'oundsof theinventionwherein the sulfolane .oiisulfolene-nucleus has only onehydr-oxy radical directly attachedto'but one nuclear. carbon atom and: has at least two alkylradicals directly attached to one or-more-nuclear carbon atoms, and particularly the 2,;-dialkylsulfolanols and ZA-diallsylsulfolenols, possess inherent. properties whiohiare-markedly superior to those of the dihydroxy cyclic sulfones such,,for examp1e,.as\3,4.- dimethyl 3,4 sulfolanediol and 2,4 di(ter-tbutyl) -3,4-sulfolanediol. These properties could not be foreseen, and they are of such a naturel as tomake'the compounds of: the invention-particularly useful in variousapplications.

Themonohydroxy polyalkylsulfolanes are prepared: by treating the corresponding polyalkylrsulfolenewith an aqueous solution'of a strong base suchas potassium hydroxide, sodium. hydioxide, or the. like. For example, a.2;4.-diaikyl e-sulfolanol is prepared by treating the correalkyl". haiosuiione:

sponding 2,4-dialkyl-3-sulfolene with an aqueous solution of sodium hydroxide at approximately room temperature, e. g. 2,4-dimethyl-3-sulfo1ene thus treated forms 2,4-dimethy1-4-sulfolanol. When a 3,4:-dia-lliyl-3-suifolene2 is treated; with an aqueous causticsolution; a 3,-4-dialkyl-3-sulfolanol is produced.

One particularly advantageous method of producing, the monohy droxy polyalkylsulfolenes of the: invention is by reaction of a polyalkyl sulfolene with hypohalogenous acid and dehydrohaloge'nationoli the; resulting monohydroxy poly- Thus, for instance, a polyalkyl sulfolenemay' be treated at about -10 C. to about 40 0., preferably at about room temperaturez witha stoichiometric excess of an aqueone solution of hypochlorous acid. On comple- 1710B: of'the reaction, the excess acid is neutralized and the product is treated with a stoichiometric excess of abase such as aqueous sodium hydroxide or. pyridine or the 1ike,the mixture being heated preieiably'to about- 25Cgto about Cito obtain. the; corresponding monohydroxy polyalkyl sulfolene. In this. way, 4-hydroxy-2,4-dimethyi= 2-sii1folenei's obtained from 3'-chl'oro4-hydroxy'- 2;,4' diinethylsulfolane produced from 2,4 dimethyhii-sulfolene, and iehydroxy-zt'i -diisopropyl-z sulfolene is recovered. in good yields from B-chloro-l-hYdioxy- 2:5 dii'sopropyl'sul fol'ane readily, obtainedfrom 2,5-diisopropyl-3- sulfol'ne. In starting with 2-methy1'-5 -ethyl-'3'- sufol'ene in thisprocess, a mixture cite-hydran- 2-methyl 5'-ethyl -25sulfolene and 3"-'liydi".oxyr-2'- methyho-ethyl-i-sulfolene is obtained. While these isomers maybe separate-dibefore; use. of the product, this is usually unnecessary as these compoundshavevery similar properties which'make them generally equallyusefulinthe applications to which the newcompound's of the-invention are adopted.

The monohydroxy polyalkyl' sulfolanes ofthe invention may also be produced by catalytic hydrogenation oi. the corresponding monohydroxy polyalkyl sulfol'enes prepared. in the foregoing manner. Active nickehparticularly R'aney nickel, at relatively low'temperature's, for instance about 208C; to 100 01, is-a'n advantageous catalyst for this hydrogenationbut other hydrogenation cataiysts may also be used;

The novel polyalkylsuli'olanols and polyalkyh sulfolenols of the invention find utility in a large variety of industries. For example, they may be used as insecticides, fungicides and parasiticides, or as ingredients of insecticidal, fungicidal and parasiticidal compositions, and as ingredients for use in the manufacture'of varnishes, polishes, and the like. The novel compounds may also be employed: in'theiprepanatiorr of natural or. synthetic rubbers, resins,.plastics, etc;, and as perfumefixatives and the; like; Moreover, the: polyalleylsuliiolanols and the polyaikylsulfolenolsmay be further reacted, e. g. sulfurized, sulfated, esterified, or the like. to: produce: valuable.- substances to be used as: addition agents in. lubricating. oils, greases, and asdetergents, aswell asior. a. variety oi other purposes.

The following examples serve to. illustrate. the invention:

Example I;

Approximately 1'46 parts by weight of 2;4'-dimethyl-3-su1fol'ene Was-dissolved in about. 3000 parts by weight of water, and tolthissolution was added about 49.4z-parts 'by'weight. of 973%. sodium hydroxide. i'm1000'. partsby 'weight of water. The solution was stirred and allowed to stand at room temperature. The reaction mixture was neutralized with HCl, evaporated to dryness, the salt cake extracted with acetone, and the solvent subsequently evaporated. The residue was distilled under reduced pressure. The 2,4-dimethyl-4 sulfolanol recovered was found to have a boiling point of 183.4" C. at 5 mm. pressure, and to have a melting point of 91.7 C. to 92.6 C.

Example Ill When a solution of about 174 parts by weight of 2,4-diethyl-3-sulfolene in about 3000 parts by weight of water is treated with about 494 parts by weight of 97.4% sodium hydroxide in 100 parts by weight of water, according to the procedure described in Example I, 2,4-diethyl-4-sulfolanol is produced in good yield.

Example III 2,4-dipropyl-4-sulfolanol from 2,4-dipropyl-3- sulfolene 2-methyl-4-ethy1-4-sulfolan0l from 2-methyl-4- ethyl-3-sulfolene 2,4-diisopropyl-4-sulfolan0l from 2,4-diisopropyl- 3-sulfolene 2,4-dlbutyl-4-sulfolanol from 2,4-dibutyl-3-sulfolene 2,5-dimethyl-3-sulfo1anol from 2,4-dimethyl-3- sulfolene 2,5-diethyl-3-sulfolanol from 2,4-diethyl-3-sulfolene 2-isopropyl-5-butyl-4-sulfolanol and z-isopropyl- -butyl-5-sulf0lano1 from 2-isopropyl-5-butyl- 3-sulfolene 3,4-diisobutyl-3-sulfolanol from 3,4-diisobutyl-3- sulfolene 3,4-diethyl-3-sulfolanol from 3,4-diethyl-3-sulfolene 2,4-dimethyl-2-sulfolanol from 2,4-dimethyi-2 sulfolene 2,5-dicyclohexyl-2-sulfolanol from 2,5-dicyc1ohexyl-Z-sulfolene 3,4-di(secondary butyl) -3-sulfolanol from 3,4-di- (secondary butyl) -2-sulfolene 2,4,5-trimethyl-4-sulfolanol from 2,4,5-trimethyl- 3-sulfolene 2,3,5-tri(tert. buty1)-3-sulfolanol from 2,3,5-tri- (tert. butyl) -3-sulfolene 2-methyl-3,5-diethyl-5-sulfolanol from 2-methyl-3,5-diethyl-4-sulfolene 2,2,4-trimethyl-4-sulfolanol from 2,2,4-trimethyl- 3-sulfolene 2,2,4-triethyl-4-sulfolanol from 2,2,4-triethyl-3- sulfolene 2,2,4,5-tetramethyl-4-sulfolanol from 2,2,4,5-tetramethyl-3-sulfolene In the same way, 2-methyl-5-phenyl-2-sulfolanol is produced from 2-methyl-5-phenyl-2-sulfolene, 2-ch1oromethyl-4-cyclohexyl-4-su1folanol is obtained from 2-chloromethyl-4-cyclohexyl-3-sulfolene and a mixture of 2-benzyl 5-styryl-3-sulfolanol and 2-benzyl-fi-styryl-e-sulfolanol is produced when 2-benzyl-5-styryl-3-sulfolene is used as the starting compound.

Example IV Into a solution of 30 parts by weight of 2,4- dimethy1-3-su1folene in approximately 800 parts 6 by weight of water, about 18 parts by weight'of chlorine was bubbled while stirring and maintaining the temperature between about 40 C. and about 50 C. When addition of the chlorine was complete, the reaction mixture was evaporated by warming under reduced pressure and subsequently distilled to obtain a good yield of 2,4-dimethyl-3-chloro-4-sulfolanol boiling between C. and 163 C. under 2mm. Hg. The 2,4-dimethyl-3-chloro-4-sulfolanol obtained is dehydrochlorinated by slowly adding it to pyridine at about 25 C. The resulting 2,4-dimethyl- 2-sulf01en-4-ol is recovered by neutralizing the reaction mixture with hydrogen chloride, evaporation of the neutralized mixture to dryness, and extraction of the residue with acetone. The 2,4- dimethyl-2-sulfolen-4-ol obtained after removal of the solvent may be recrystallized from ether.

Hydrogenation of the 2,4-dimethyl-2-sulfolene 4-01 in the presence of Raney nickel or platinum catalyst at about 25 C. under 20-30 pounds of hydrogen pressure gives the 2,4-dimethy1-4-sulfolanol obtained in Example I.

By the method of Example IV using either aqueous sodium or potassium hydroxide or pyridine as the base, other new'monohydroxy polyalkyl sulfolenes are obtained by the use of the indicated difierent starting materials: 2,5-dimethyl-2-sulfo1en-4-o1 from 2,5-dimethyl-3- chloro-4-sulfolanol obtained from 2,5-dimethyl- 3-sulfolene; 2,3-dimethyl-4-sulfolen-3-01 from 2,3-dimethyl-4-ch10ro-3-su1f01ano1 obtained from 2,3-dimethyl-3-sulfolene; 3,4-dimethyl-2-sulfolen-i-ol from 3,4-dimethyl-3-chloro-4-sulfolanol obtainable from 3,4-dimethyl-3-sulfolene; 2- methyli-ethy1-3-sulfolen-2-ol from 2-methyl- 4-ethyl-3-chloro-2-sulfolanol obtainable from 2 methyl-4-ethyl-2-sulfolene; 2,5-dipropyl-3-sulfo1en-2-ol from 2,5-dipropyl-3-chloro-2-sulfolanol obtainable from 2,5-dipropyl-2-sulfolene;

2,3,5-trimethyl-4-sulfolen-3-ol from 2,3,5-trimethyl-3-chloro-4-sulfolanol obtained from 2,3,5-trimethyl-3-sulfolene; and 2,3,4-trimethyl- 2-sulfolen-4-ol and 2,3,4-trimethyl-4-sulfo1en-3- 01 from the chlorohydrins of 2,3,4-trimethyl-3- sulfolene.

The same method of dehydrochlorination applied to 3-methyl-4-ethyl-3-chloro-2-sulfolanol gives 3-methyl-4-ethyl-3-su1folen-2-ol, and with 3-ethyl-5-methyl-3-ch1oro-2-su1folanol gives 3- ethyl-5-methyl-3-sulfolen-2-ol. In the same way 2,3-diisopropyl-3-sulfolen-5-ol is obtained from 2,3-diisopropyl-4-chloro-5-sulfo1anol and 2,3-dimethyl-3-sulfolen-2-ol is obtained from 2,3-dimethyl-3-chloro-2-sulfolanol and 2,3-diethyl-2- sulfolen-5-ol is produced from 2,3-diethyl-3- chloro-5-sulfolanol.

Still other novel monohydroxy polyalkyl sulfolanes and sulfolenes which may be prepared include, for instance, 2,4-dimethyl-3-sulfo1anol, 2,4-diethyl-3-sulfolanol, 3,4-dimethyl-2-sulfolanol, 2-isopropyl-4-butyl-3-sulfolanol, 2,4-dimethyl-2-sulfolen-5-ol and 2,4-diisopropyl-2-sulfolen-5-ol.

We claim as our invention:

1. A compound containing a five-membered heterocyclic nucleus consisting of four nuclear carbon atoms and one sulfonyl radical wherein at least two of the nuclear carbon atoms of said heterocyclic nucleus are directly attached to alkyl radicals and wherein one of the nuclear carbon atoms of said heterocyclic nucleus is directly attached to the hydroxy radical, the remaining free bonds of the nuclear carbon atoms of said heterocyclic nucleus being directly attached to members ausaam L inf thergroup consisting-of the hydrogen-iatemzand theihydrocanhoniradicals.

2. A compound containing a zfive-membered ih'e'terocyclic mucleus consisting :of tour nuclear carbon :atoms and tone :sulfonyl radical wherein 'each -.o'f :two :nuclear carbon atoms of asaidhetero- ,cydlic nucleus ;is [directly attached to an alkyl radical and wherein tone of 113116 nuclear carbon :a'toms=tof said iheterocyclic nucleus is directly attach'e'd'to the hydroxyradical, the rema'iningdre'e bonds of the :nuclear carbon-atoms of :sai'dl-h'etero- -cyclic nucleus being directly attached to hydrogen atoms.

13.:A compound containing a 'five-lmenibered heterocyclic nucleus rconsis'tingcf Tour saturated nuclear carbon :atoms and zone :sulfonyl radical wherein each of the :nuclear carbon :atoms iin'the 2- and l-positions :of said :heterocyclic nucleus is directly-attached to an alkyl radical and'wherein one of the nuclear carbon :atoms of said hetero- -'cyclic nucleus once removed from .the 'sulfonyl radical thereof is linked :directly to the lrydmxy radical, the remaining-free bonds of the nuclear carbon atoms *being directly :attached to the hy- *drogen atoms f said heterocyclic nucleus.

-4. 2;4-dimethyl 3-sulfolanol of the formula :rectly attached :toalkyl radicals and wherein-one of the nuclear carbon atoms of said heterocyclic nucleus is linked directly to the hydroxy radical,

the remaining :free bonds of the :nuclear :carbon 0 .atoms of :said heterocyclic nucleus being directly attached to hydrogen atoms.

'7. A compound containing a .five-membered heterocyclic nucleus consisting of four nuclear carbon atoms and one sul'fonyl radical and containing a double bond "between the two nuclear carbon atoms once removed from the sul fonyl radical of said-heterocyclic nucleus, wherein each of the nuclear carbon atoms in the 2- and the 4-positions of said 'heterocyclic nucleus is directly attached to an alkyl radical and wherein a nuclear carbon atom directly lin'ked'to saidsul'fo'nyl radical of said heterocyclic nucleus is directly attached to the hydroxy radical, the remainingfree bonds of the nuclear carbon atoms of said 'heterocyclic nucleus being directly linked to hydrogen atoms.

"'8. 2,4-dimethyl-2-sulfolen-l-ol of the formula :9. Aprocess forthe-productlonof a 2,4-dialkyll+su1fo1ano1 of the formula OH .H=c--t-R' R4 H 1 3112 0 o wherein R and R represent alkyl radicals of not more than '4 carbon atoms which comprises -reacting a 2,4-dialkyl-3-sulfol6ne of the formula wherein R and R represent .alkyl radicals of not more than 4 carbon atoms in an aqueous caustic solution.

10. A process for the production of '2,'4-dimethyl-fi-sulfolanol of the formula which comprises treating 2,4-dimethyl-3-suliolenelof the .iomnula with an aqueous solution of sodium hydroxide at a'tempera'ture of about '25" C.

11. A 2,4-dialkyl-4-sulfolanol of the'formula HaC-C )R' R- H (3112 S r s tached to member-sci thegroup consisting :of the hydrogen atom and the hydrocarbon radicals.

RUPERT C. MORRIS. NORTEN C. MELCHIOR.

CETED The'following references are of record .in the .file of this patent:

*UNI'IED STATES PATENTS Number Name Date 2,189,367 Muth Feb. 6, 1940 12,393,925 Morris et al Jan. 29, $946 

